Functionalized two-dimensional carbon fillers for enhancing Li+ conduction and interface stability of solid electrolyte for lithium batteries

Currently, electrolytes used in lithium-ion batteries are flammable and leaky, causing safety problems when used under high temperatures or extreme conditions. Solid electrolytes can fundamentally avoid the occurrence of such issues, at the same time, it can significantly increase the energy density of solid state lithium batteries. Solid electrolytes are classified into inorganic solid electrolytes and solid polymer electrolytes. Although inorganic solid electrolytes have the high mechanical strength and room temperature ionic conductivity, it has poor flexibility and complicated preparation process. In contrast, solid polymer electrolyte has good elasticity and good interface contact, which can overcome many disadvantages of the inorganic solid electrolyte. Among them, polyethylene oxide (PEO) is first proposed as a polymer electrolyte. Due to its excellent mechanical properties, electrochemical stability and thermal stability, it has been a hot topic for polymer solid electrolytes for decades. However, its low room temperature ionic conductivity limits practical application. Given the problems existing in PEO-based polymer electrolytes, several methods for improving ionic conductivity have been proposed. The primary methods include plasticization, the organic-inorganic composite, and polymer blending. Comparing these methods, it can be seen that adding plasticizers to the polymer can effectively increase the conductivity of the electrolyte, but at the same time it will cause a decrease in the mechanical properties, and the safety issues limit its application in lithium-ion batteries. Inorganic fillers can balance the problems of ionic conductivity and mechanical properties, but the construction of a good filler-polymer dispersion system is complicated in preparing such composite electrolytes, design a new type of multi-dimensional the ion transport network also face tremendous challenges. Undoubtedly, in the future research, inorganic fillers will be the dominant means in the modification of composite electrolytes. Compared with the former two modification methods, polymer blending is easy to operate and friendly to industry, but low ionic conductivity at room temperature still exist. To give full play to the advantages of polymer blending, using it as an auxiliary means to improve the performance of composite electrolytes will be the primary development direction of such modification methods. PEO is the most widely studied polymer electrolyte. Even though a large number of modification methods have emerged in its development history, the ionic conductivity at room temperature is still limited to a relatively low level. To meet the needs of the application in lithium-ion batteries, a high operating temperature (50−70℃) is still needed, the biggest problem remains exist. To solve the problems in polymer solid electrolytes, the research directions in the future may mainly focus on: Expanding the modification method of PEO to other polymer electrolyte host materials, broadening the scope of research, and finding the available polymer electrolytes at room temperature. Concerned about the preparation of ultra-thin polymer electrolytes, reducing the ion transmission path to increase the transmission efficiency of lithium ions between positive and negative electrodes. Effectively combines inorganic solid electrolytes and solid polymer electrolytes to give full play to their advantages. In addition, exploring the effect of inorganic filler morphology on the conductivity of the composite electrolyte will also deserve attention. Many one-dimensional, two-dimensional materials can build ion transport networks so that lithium ions can travel rapidly along the path. With the deepening of research, it is expected that PEO-based polymer electrolytes may replace liquid electrolytes and become an essential cornerstone for building the next generation of safe and reliable lithium-ion batteries.

In this study, solvent‐free nanofibrous electrolytes were fabricated through an electrospinning method. Polyethylene oxide (PEO), lithium perchlorate and ethylene carbonate were used as polymer matrix, salt and plasticizer respectively in the electrolyte structures. Keggin‐type hetero polyoxometalate (Cu‐POM@Ru‐rGO, Ni‐POM@Ru‐rGO and Co‐POM@Ru‐rGO (POM, polyoxometalate; rGO, reduced graphene oxide)) nanoparticles were synthesized and inserted into the PEO‐based nanofibrous electrolytes. TEM and SEM analyses were carried out for further evaluation of the synthesized filler structures and the electrospun nanofibre morphologies. The fractions of free ions and crystalline phases of the as‐spun electrolytes were estimated by obtaining Fourier transform infrared and XRD spectra, respectively. The results showed a significant improvement in the ionic conductivity of the nanofibrous electrolytes by increasing filler concentrations. The highest ionic conductivity of 0.28 mS cm−1 was obtained by the introduction of 0.49 wt% Co‐POM@Ru‐rGO into the electrospun electrolyte at ambient temperature. Compared with solution‐cast polymeric electrolytes, the electrospun electrolytes present superior ionic conductivity. Moreover, the cycle stability of the as‐spun electrolytes was clearly improved by the addition of fillers. Furthermore, the mechanical strength was enhanced with the insertion of 0.07 wt% fillers to the electrospun electrolytes. The results implied that the prepared nanofibres are good candidates as solvent‐free electrolytes for lithium ion batteries. © 2020 Society of Chemical Industry

The poor operational stability of electrolytes is a persistent impediment in building redox flow battery technology; choosing suitable stability additives is usually the research direction to solve this problem. The effects of five phosphate containing additives (including 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), hexamethylene diamine tetramethylene phosphonic acid (HDTMPA), amino trimethylene phosphonic acid (ATMPA), sodium ethylenediamine tetramethylene phosphonate (EDTMPS), and diethyl triamine pentamethylene phosphonic acid (DTPMP)) on the thermal stability and electrochemical performance of the positive electrolyte of vanadium redox flow battery were investigated. With 0.5 wt% addition, most of the selected additives were able to improve the thermal stability of the electrolyte. HEDP and HDTMPA extended the stability time of the pentavalent vanadium electrolyte at 50 °C from 5 days (blank sample) to 30 days and 15 days, respectively. The electrochemical performance of the electrolyte was further investigated by cyclic voltammetry, steady state polarization, and electrochemical impedance spectroscopy tests. It was found that most of the additives enhanced the electrochemical activity of the positive electrolyte, and the diffusion coefficients, exchange current densities, and reaction rate constants of V(IV) species became larger with the addition of these additives. It is verified that the thermal stability and electrochemical stability of the electrolyte are significantly improved by the combination of ATMPA + HEDP or ATMPA + HDTMPA. This study provides a new approach to improve the stability of the positive electrolyte for vanadium redox flow battery.

In the present study, we report a preparation of a new category of gel polymer electrolytes by immobilizing various compositions of lithium nonafluoro-1-butanesulfonate (LiNfO) salt and less viscous 1-ethyl-3-methylimidazolium nonafluoro-1-butanesulfonate (EMImNfO) ionic liquid in polyvinylidenefluoride-co-hexafluoropropylene (PVdF-co-HFP) matrix for their application in lithium ion batteries. Our study reveals that composition with 80% EMImNfO-LiNfO + 20% PVdF-co-HFP composition has the highest ionic conductivity of 10−2 S cm−1. The performance characteristics of highly conducting ionic liquid incorporated gel polymer electrolyte (ILGPE) is evaluated by using different electrochemical techniques such as chronoamperometry, cyclic voltammetry, and lithium compatibility test. ILGPEs exhibit excellent properties and will facilitate its use as a potential separator for lithium ion batteries.

Co-doping strategy enhanced the ionic conductivity and excellent lithium stability of garnet-type Li7La3Zr2O12 electrolyte in all solid-state lithium batteries

Solid polymer electrolytes for bipolar lithium ion batteries requiring electrochemical stability of 4.5 V vs. Li/Li+ are presented. Thus, imidazolium-containing poly(ionic liquid) (PIL) networks were prepared by crosslinking UV-photopolymerization in an in situ approach (i.e., to allow preparation directly on the electrodes used). The crosslinks in the network improve the mechanical stability of the samples, as indicated by the free-standing nature of the materials and temperature-dependent rheology measurements. The averaged mesh size calculated from rheologoical measurements varied between 1.66 nm with 10 mol% crosslinker and 4.35 nm without crosslinker. The chemical structure of the ionic liquid (IL) monomers in the network was varied to achieve the highest possible ionic conductivity. The systematic variation in three series with a number of new IL monomers offers a direct comparison of samples obtained under comparable conditions. The ionic conductivity of generation II and III PIL networks was improved by three orders of magnitude, to the range of 7.1 × 10−6 S·cm−1 at 20 °C and 2.3 × 10−4 S·cm−1 at 80 °C, compared to known poly(vinylimidazolium·TFSI) materials (generation I). The transition from linear homopolymers to networks reduces the ionic conductivity by about one order of magnitude, but allows free-standing films instead of sticky materials. The PIL networks have a much higher voltage stability than PEO with the same amount and type of conducting salt, lithium bis(trifluoromethane sulfonyl)imide (LiTFSI). GII-PIL networks are electrochemically stable up to a potential of 4.7 V vs. Li/Li+, which is crucial for a potential application as a solid electrolyte. Cycling (cyclovoltammetry and lithium plating-stripping) experiments revealed that it is possible to conduct lithium ions through the GII-polymer networks at low currents. We concluded that the synthesized PIL networks represent suitable candidates for solid-state electrolytes in lithium ion batteries or solid-state batteries.

Strategies for improving ionic conductivity and mechanical stability of solid polymer electrolytes for lithium batteries via physical and chemical interlocking

Study on ionic conductivity of polymer electrolyte plasticized with PEG–aluminate ester for rechargeable lithium ion battery

The copper current collector is an important component for lithium-ion batteries and its stability in electrolyte impacts their performance. The decomposition of LiPF6 in the electrolyte of lithium-ion batteries produces the reactive PF6, which reacts with the residual water and generates HF. In this paper, the adsorption and dissociation of H2O, HF, and PF5 on the Cu(111) surface were studied using a first-principles method based on the density functional theory. The stable configurations of HF, H2O, and PF5 adsorbed on Cu(111) and the geometric parameters of the admolecules were confirmed after structure optimization. The results showed that PF5 can promote the dissociation reaction of HF. Meanwhile, PF5 also promoted the physical adsorption of H2O on the Cu(111) surface. The CuF2 molecule was identified by determining the bond length and the bond angle of the reaction product. The energy barriers of HF dissociation on clean and O-atom-preadsorbed Cu(111) surfaces revealed that the preadsorbed O atom can promote the dissociation of HF significantly.

During this reporting period a number of novel solid polymer electrolytes formed by salts of multivalent cations and poly(ethylene oxide) (PEO) have been prepared and characterized. These materials are of interest not only because of their potential ionic conductivities, but also because some of them may have electronic conductivity and oxidizing power which would be useful for novel electrode materials in all-solid-state batteries. Two broad classes of materials were investigated: PEO solutions of Zn(II), Cd(II), and Pb(II), all of which are potential electrolytes for solid-state batteries, and PEO solutions of transition metal salts, which are of interest as possible cathode materials. Mixed compositions containing both divalent cations and lithium ions were also prepared. Electrolytes formed with small, highly-polarizing ions, such as Mg(II) and Ca(II), are essentially pure anion conductors. Electrolytes containing Zn(II) behave similarly, unless they are hydrated, in which case the Zn(II) ions are quite mobile. Electrolytes formed with larger, more polarizable cations, such as Pb(II) and Cd(II), conduct both anions and cations. Solutions of salts of transition metal cations form a third group of electrolytes. Of the electrolytes investigated so far, those formed with Ni(II) salts are the most unusual. It appears as if the transport number of Ni/sup + +/ and the electrolyte conductivity can be greatly enhanced by controlling the hydration and dehydration of the polymer. 10 refs., 9 figs., 1 tab.

A green and environmentally friendly polymer, methyl cellulose (MC), is used as a host matrix of a gel polymer electrolyte for lithium ion batteries. It shows good mechanical performance and thermal stability. The ionic conductivity of the gel polymer electrolyte is 0.20 mS cm−1 and it has a higher lithium ion transference number (t+ = 0.29) than the commercial separator (0.27). When evaluated using LiFePO4 as cathode and Li metal as the counter and reference electrode, the LiFePO4 cathode exhibits relatively higher reversible capacity for the gel polymer electrolyte than that for the commercial separator. In addition, the rate capability and cycling performance are also comparable with those for the commercial separator. This provides another direction for gel polymer electrolytes and environmental protection.

An extrapolation method is usually applied when Ab initio molecular dynamics (AIMD) is applied to studying ionic conductivity in solid-state electrolytes in lithium-ion batteries. As the ions move slowly in solid-state electrolytes, the first-principles method typically involves computationally intensive calculations, and it can take significant time to obtain accurate results. First-principles method is too expensive for the time scale required at room temperature. The classical molecular dynamics method is typically applied to systems containing thousands of atoms and can simulate the system’s behavior over nanoseconds. During the simulation, the positions and velocities of the atoms are updated at discrete time intervals, allowing the system’s behavior to be studied over time. However, its accuracy depends on the empirical force-field libraries. Limited by the computational resource, the previous studies applied the extrapolation method to obtain the room temperature ionic conductivity, which was not accurate because the linear relationship in the Arrhenius equation was not valid in a wide range of temperatures. Deepmd-Kit is a tool that integrates these two different computational approaches. The extrapolation and Deepmd methods were applied to the materials Li10GeP2S12, Li10SiP2S12, Li10GePS12Cl, and Li10SiPS12Cl, respectively. Both methods showed that the lithium ions favor the c direction when diffusing in the LGPS-type solid-state electrolytes. The ionic conductivity is more accurate with the dependent method compared with experiments.

Solid-state lithium-ion batteries with high safety are the encouraging next-generation rechargeable electrochemical energy storage devices. Yet, low Li+ conductivity of solid electrolyte and instability of solid-solid interface are the key issues hampering the practicability of the solid electrolyte. In this research, core-shell MOF-in-MOF nanopores UIO-66@67 are proposed as a unique bifunctional host of ionic liquid (IL) to fabricate core-shell ionic liquid-solid electrolyte (CSIL). In the current design of CSIL, the shell structure (UIO-67) has a large pore size and a high specific surface area, boosting the absorption amount of ionic liquid electrolyte, thus increasing the ionic conductivity. Nevertheless, the core structure (UIO-66) has a small pore size compared to the ionic liquid, which can confine the large ions, decreasing their mobility, and selectively boost the transport of Li+ . The CSIL solid electrolyte exhibits considerable enhancement in the lithium transference number (tLi + ) and ionic conductivity compared to the homogenous porous host (pure UIO-66 and UIO-67). Additionally, the Li|CSIL|Li symmetric batteries maintain a stable polarization of less than 28mV for more than 1000 h at 1000 µA cm-2 . Overall, the results demonstrate the concept of core-shell MOF-in-MOF nanopores as a promising bifunctional host of electrolytes for solid-state or quasi-solid-state rechargeable batteries.

Effect of mixed LiBOB and LiPF 6 salts on electrochemical and thermal properties in LiMn 2O 4 batteries

There is considerable interest in developing solid electrolytes for rechargeable lithium batteries as they have the potential to increase both energy density due to incorporation of a lithium metal anode and safety of batteries due to the fact that they are nonflammable. Block copolymers with a mechanically hard non-conducting block and a soft ion-conducting block provide an avenue for obtaining highly conducting rigid solids. In this study we add surface-modified TiO2 nanoparticles to a mixture of polystyrene-block-poly(ethylene oxide) and bis(trifluoromethane)sulfonimide lithium salt. The presence of BF4− moieties on the surface of the particles was essential for obtaining macroscopically homogeneous electrolytes; macrophase separation was observed with the same nanoparticles with surfaces covered with oleic acid. The stability of these composite electrolytes against lithium metal electrodes was tested in symmetric lithium-composite electrolyte-lithium cells. The surprising result was that electrolytes with 24 wt% nanoparticles exhibited optimum stability; the amount of charge passed before dendrite formation observed in the optimized composite electrolyte was a factor of 4.7 larger than that of the neat block copolymer electrolyte. Both tensile and shear moduli of the electrolytes were non-monotonic functions of particle concentration with peaks in the vicinity of 17 to 20 wt%.